Protection of organic material from oxidative deterioration with bis-(3, 5-dihydrocarbyl-4-hydroxybenzyl) sulfoxides



United States Patent 3,322,649 PROTECTION OF ORGANIC MATERIAL FROM OXIDATIVE DETERIORATION WITH BIS- (3,5 DIHYDROCARBYL 4 HYDROXYBEN- ZYL) SULFOXIDES Francis X. DShea, Wolcott, Conn., assignor to Uniroyal, Inc., a corporation of New Jersey No Drawing. Original application May 25, 1960, Ser. No. 31,542, now Patent No. 3,272,869, dated Apr. 13, 1966. Divided and this application Nov. 1, 1960, Ser. No.

3 Claims. (Cl. 202-404) ABSTRACT OF THE DISCLOSURE Bis-(3,5 dihydrocarbyl-4-hydroxybenzyl) sulfides and sulfoxides are used in relatively small amounts to protect organic materials such as elastomers, polyamides, polyolefins, fats, petroleum products such as gasoline and turbine oils, and synthetic lubricants against oxidative deterioration. Methods for the synthesis of these antioxidants are also disclosed This is a division of my copending application Ser. No. 31,542, filed May 25, 1960.

This invention relates to a new series of compounds referred to broadly as bis-(3,5-dihydrocarbyl-4-hydroxybenzyl)sulfides and the corresponding sulfoxides, which are useful as essentially nondiscoloring, nonstaining antioxidants for organic materials normally subject to oxidative deterioration such as elastomers, polyamides, polyolefins, fats, petroleum products and synthetic lubricants. The compounds of the invention are derived from 2,6- dihydrocarbylphenols and may be represented by the formula:

R R l I 11 ocmxcnon kl BE! in which R and R are alkyl, cycloalkyl or aralkyl radicals containing less than 13 carbon atoms and X is a bivalent sulfur atom or the bivalent radical The compounds may be prepared by several methods. A convenient synthesis is the reaction of a 2,6-dihydrocarbyl-4-(dialkylaminomethyl)phenol or a suitable quaternary salt thereof with an alkali metal sulfide, for example:

l Hoornscm-Q-on no-Q-cmmonofir Nals 3,322,649 Patented May 30, 1967 "ice The sulfoxide compounds are prepared from the sulfides by oxidation according to classical procedures, for example, with hydrogen peroxide in glacial acetic acid.

The invention ditfers from the prior art in the following ways:

(1) The series of compounds of this invention is previously unreported. Such compounds are herein disclosed for the first time.

(2) Unlike the products described by L. A. Mikeska and A. R. Kittleson in US. Patents Nos. 2,415,833 and 2,488,134, the compounds of the present invention are of known composition and purity, usually readily isolated in crystalline form. The use of a dihydrocarbylphenol as starting material avoids the formation of undesirable resins and more highly condensed structures of the type found in the examples of Mikeska 0nd Kittleson. Additionally, the compounds of the present invention contain the bridging group para to the phenolic hydroxyl. The superior antioxidant properties of the para-bridged compounds compared to the ortho-bridged compounds are apparent in the working examples to follow.

(3) In contrast to the products described by both Mikeska and Kittleson in US Patent Nos. 2,415,833 and 2,488,134, and by Mikawa in Bull. Chem. Soc, Japan, 27, 50 (1954); 0A., 49, 9274C, the compounds of the invention contain hydrocarbyl radicals ortho to the phenolic hydroxyl radical. This structural feature, especially when the hydrocarbyl radicals are bulky, gives the compounds superior antioxidant activity in many a plications.

(4) Several of the compounds of the invention may be prepared directly from the dihydrocarbylphcnols by a novel, practical, one-step synthetic method as described herein.

Methods of carrying out the im'enti0vz.-(I) The compounds of the invention may be prepared by treating one molar equivalent of a compound of the formula,

where R and R are alkyl, cycloalkyl or aralkyl groups of up to about twelve carbon atoms and R" is an alkyl group, with 0.5 molar equivalent of an alkali metal sulfide in a suitable solvent at from 50 C. to about C. The amine compounds are prepared by treating a dihydrocarbylphenol with formaldehyde and a dialkylamine in the ordinary Mannich type reaction.

The dihydrocarbylphenols which may be used include 2,6 xylenol; 2 methyl-6-t-butylphenol; 2,6-diisopropylphenol; 2,6 di t butylphenol; 2-methy1-6-cyclohexyl- 3 phenol; 2,6 dicyclohexylphenol; 2 methyl-6-t-octylphenol; 2,6-di-t-octylphenol; 2-methyl-6-(alpharnethylbenzyl) phenol; 2,6-di-(alpha-methylbenzyl)phenol; 2-methyl-6- dodecylphenol; etc.

Any dialkylamine may be used but the low molecular weight members such as dimethylamine are preferable since the subsequent displacement reaction can be followed by evolution of the volatile amine product.

The reaction With the alkali metal sulfide is preferably carried out in a refluxing alcoholic solvent such as methanol, ethanol, isopropanol, ethylene glycol monoethyl ether, etc. The preferred alkali metal sulfide is sodium sulfide.

The compounds may also be prepared by reaction of a quaternary salt of the dihydrocarbyl-(dialkylaminomethyl)phenol with an alkali metal sulfide. Salts with methyl iodide are examples.

The sulfoxide compounds of the invention are prepared from the sulfides by oxidation according to classical procedures, for example, with hydrogen peroxide in glacial acetic acid.

(II) The compounds of the invention derived from hindered 2,6-dihydrocarbylphenols may be prepared directly from the phenols by a novel, one-step method. The method involves reacting a molar proportion of the phenol with one to about three molar proportions of formaldehyde and 0.5 to about two molar proportions of an alkali metal sulfide or hydrosulfide in an alcoholic solvent at about 25 C. to 150 C.

Examples of suitable phenols which may be employed in this novel reaction are 2-methyl-6-t-butylphenol; 2,6- diisopropylphenol; 2,6-di-t-butylphenol; 2,6-dicyclohexylphenol; 2methyl-6-t-octylphenol; 2,6-di-t-octylphenol; 2- methyl-6-(alpha methylbenzyl)phenol; 2,6 di (alphamethylbenzyl)phen-ol; 2-methyl-6-dodecylphenol; etc.

The formaldehyde may be an aqueous solution or in the form of para-formaldehyde. Examples of the alkali metal sulfide and hydrosulfide are Na S, K S, NaSH, KSH, etc.

The most suitable solvents for the reaction are methanol, ethanol, isopropanol and ethylene glycol monoethyl ether. Methanol is the preferred solvent since it allows solubility of the reactants and, in many cases, crystallization of the product directly from solution. The reaction is most conveniently carried out at the reflux temperature of the solvent for from 0.5 to about 24 hours. In those cases where the product does not precipitate on cooling, it may be readily isolated by removal of the solvent or by dilution with water. Liquid products may be isolated in this manner.

EXAMPLE 1 Preparation bis-(3,5-di-t-buryl-4-hydroxybenzyl) sulfide 2,6-di-t-butylphenol (134 g., 0.65 mole), 100 ml. (1.23 moles) of 37% aqueous formaldehyde and 120 g. (0.5 mole) of sodium sulfide nonahydrate were dissolved in one liter of methanol in a 2-liter, 3-neck flask fitted with a stirrer, a condenser and a gas-inlet tube. The solution was saturated with a constant stream of nitrogen and heated to reflux for 30 minutes. During reflux a crystalline product began to precipitate. The mixture was cooled in ice and filtered. The white precipitate was washed well with water and dried in a 60 Oven, yield=138 g. (90.2%) M.P.=l41-142 C. A sample recrystallized from methanol had M.P.=142143 C.

Analysis.Calcd: C, 76.60; H, 9.85; S, 6.82. Found: C, 76.80; H, 9.74; S, 6.58.

EXAMPLE 2 Preparation of bis-(3,5-di-t-butyl-4-hydr0xybenzyl) sulfoxzde Bis (3,5-di-t-butyl-4-hydroxybenzyl)sulfide (58.7 g., 0.125 mole) was dissolved in one liter of glacial acetic acid with slight warming. The solution was cooled to 30 C. and 14.2 g. (0.125 mole) of 30% hydrogen peroxide was added in small portions. The temperature rose to 35 during the addition. The solution was allowed to stand at room temperature for three hours and was then diluted with 3 liters of ice water. The white solid precipitate was filtered, washed well with water, and dried, wt.=61 g. (quantitative), M.P.=149-154 C.

EXAMPLE 3 Preparation of bis-(3-methyl-4-hydr xy-5-t-butylbenzyI) sulfide Z-methyl-G-t-butylphenol (410 g., 2.5 moles), 205 g. (2.5 moles) of 37% aqueous formaldehyde and 300 g. (1.25 moles) of Na S-9H O were dissolved in a mixture of ml. of water and 600 ml. of methanol in a 2-liter, 3-neck flask fitted with a stirrer, condenser and thermometer. The solution was refluxed for one hour. The methanol was then distilled off and the aqueous layer decanted off the viscous product. The product was then rinsed with water and extracted with ether. The ether extract was washed with water, dilute hydrochloric acid and water. The organic layer was then evaporated down to a pale yellow solid product, yield=449 g. (93%). Recrystallization from aqueous methanol gave crystalline bis-(3-methyl-4-hydroxy-S-t-butylbenzyl)sulfide, M.P.=ll6-ll7 C.

Analysis.Calcd: C, 74.60; H, 8.87; S, 8.28. Found: C, 75.06; H, 8.90; S, 8.11.

EXAMPLE 4 Preparation of bis-(3-methyl-4-hydroxy-5-t-butyIbenzyl) sulfoxide Bis (3-rnethyl-4-hydroxy-5-t-butylbenzyl)sulfide (31.2 g., 0.08 mole) was oxidized with 9.6 g. (0.08 mole) of 30% hydrogen peroxide in 500 ml. of glacial acetic acid as described in Example 2. Bis-(3-methyl-4-hydroxy-5-tbutylbenzyl)su1foxide was obtained in quantitative yield, M.P.=l70-l75 (dec.) raised to (dec.) after washring with warm chloroform.

AnaIysis.-Calcd: S, 7.97. Found: S, 7.93.

EXAMPLE 5 Preparation of bis-(3,5-dimethyl-4-hydroxybenzyl) sulfide 2,6-dimethyl-4-(dimethylaminomethyl)phenol (17.9 g., 0.1 mole) was refluxed under a stream of nitrogen with 12 g. (0.05 mole) of Na S-9H O in 100 ml. of ethylene glycol monoethyl ether for six hours. The evolution of dimethylamine could be detected during the reflux period. The solution was then cooled and diluted with water containing 0.1 mole of HCl. The precipitated solid product was filtered 01f, dried and recrystallized twice from benzene affording 8.5 g. (56%) of bis-(3,5-dimethyl-4-hydroxybenzyl)sulfide, M.P., 100401".

Analysis.-Calcd: C, 71.52; H, 7.35; S, 10.60. Found: C, 72.80; H, 7.32; S, 10.17.

EXAMPLE 6 Preparation 0 bis- (3,5-dicyclohexyl-4- hydroxybenzyhsulfide 1,6-dicyc1ohexylphenol (25.8 g., 0.1 mole) was refluxed with 16 g. (0.2 mole) of 37% aqueous formaldehyde and 18 g. (0.075 mole) of Na S-9H O in 65 ml. of methanol for one hour. The mixture was filtered and the filtrate was poured into a large volume of cold water. The resultant precipitate was filtered off and dried affording 32 g. (76%) of bis-(3,5-dicyclohexyl-4-hydroxybenzyl)sulfide, M.P. l30-132 after crystallization from benzene.

AnaIysis.Calcd: S, 5.56. Found: S, 6.18.

EXAMPLE 1 Preparation of bis-[3-methyl-4-hydroxy-5- (alpha-methylbenzyl)benzyl]sulfide 2-methyl-6-(alpha-methylbenzyl) phenol (42.4 g., 0.2 mole) was refluxed with 16.2 g. (0.2 mole) of 37% aqueous formaldehyde and 24 g. (0.1 mole) of Na S-9H O in 150ml. of methanol for one hour. The mixture was poured into a large volume of cold water yielding bis-[3-methyl- 4-hydroxy-5-(alpha-methylbenzyl)benzyl]sulfide, an amber viscous liquid.

EXAMPLE 8 This example demonstrates the usefulness of the compounds as fat antioxidants using the Schaal oven aging test. Prime steam pork fat, 150 g., was melted and 15 mg. of the chemical mixed in. A peroxide number by the potassium iodide-starch method was then taken as the zero reading. The samples were placed in a 60 C. oven and readings were taken after 3 days and then at one week intervals. A peroxide number of 30 is considered to be failure.

Compound: Days to failure (1) Blank 3 (2) 2,6-di-t-butyl-4-methylphenol 11-24 (3 Bis- 3,5 -di-t-butyl-4-hydr0xybenzyl)sulfoxide 11-24 (4) Bis-(3-methyl-4-hydr0xy-5-tbutylbenzyl)sulfoxide 24-32 (5) Bis- 3 ,5 -di-t-butyl-4-hydroxybenzyl)sulfide 32-38 (6) Bis-(3-methyl-4-hydroxy-5-tbutylbenzyl)sulfide 38-46 (7) Bis-(3,5-dimethyl-4-hydroxybenzyl)sulfide 46 A comparison of my compounds with a leading commerical antioxidant (2) is shown.

EXAMPLE 9 Several compounds were evaluated as fat antioxidants in the Schaal oven test as described in Example 8.

Compound: Days to failure (1) Bis-(4-hydroxybenzyl)sulfide 17-25 (2) Bis-(2-hydroxy-3-t-butyl- 5-methylbenzyl)sulfide 7-17 (3) Bis-(3,5-dimethyl-4-hydroxybenzyl)sulfide 39-52 (4) Bis-(3-methyl-4-hydroxy-5-tbutylbenzyl)sulfide 39-52 This example demonstrates the superiority of my compounds to a corresponding ortho-bridged compound (2) and to a para-bridged compound containing no ortho substituents (1).

EXAMPLE 10 This example demonstrates the usefulness of the compounds as antioxidants for polyethylene. The compound was milled into uninhibited polyethylene on the basis of 0.1 part of the antioxidant per 100 parts of polyethylene. A sample film of 5-mil thickness was pressed out and placed in an oven at 140 C. Infra-red absorption spectra of the samples revealed a sharp carbonyl development at a time coinciding with visual degradation.

Compound: Hours to failure (1 Blank 8 (2) Bis-(3,5-dimethyl-4-hydroxybenzyl sulfide 72 (3) Bis-(3,5-diisopropyl-4-hydroxybenzyl sulfide 72 (4) Bis-(3-methyl-4'hydroxy- 5-t-butylbenzyl)sulfide 80 (5) Bis-( 3-methyl-4-hydroxy- S-t-butylbenzyl)sulfoxide 80 6 EXAMPLE 11 A sample of polyethylene containing 0.1% of the antioxidant was placed in an oxygen absorption apparatus at 140 C. The length of the induction period preceding rapid absorption of oxygen was observed.

Compound: Induction period, hours (1) Blank 24 (2) Bis-(3-methyl-4-hydroxy-5- t-butylbenzyl)sulfide 450 EXAMPLE 12 A natural rubber composition was prepared in accordance with the following recipe:

The antioxidants (1 part) were then milled into 233.65 parts of masterbatch No. 1 and samples were cured at 274 F. for 30 minutes. Tensile bars were aged in an oxygen bomb for 96 hours at 70 C. The percent retention of tensile strength after aging demonstrates the activity of the compounds as rubber antioxidants.

Compound: Percent tensile retained (1) Blank 6 (2) Bis-(4-hydroxybenzy1)sulfide 14 (3) Bis-(2-hydroxy-3-t-buty1-5- methylbenzyl)sulfide l4 (4) Bis-(3,5-dimcthyl-4-hydroxybenzyl)sulfide 63 (5) Bis-(3methyl-4-hydroxy-5-tbuty1benzyl)sulfoxide 68 (6) Bis-(3,S-di-t-butyl-4-hydroxybenzyl)sulfide 79 (7) Bis-(3,-methyl-4-hydroxy-5-tbutylbenzyl)sulfide -2 93 (8) Antioxidant A Comparison to a commercial alkylated bis-phenol type antioxidant (8) is shown. The example also demonstrates the superiority of my compounds to a corresponding ortho-bridged compound (3) and to a para-bridged compound containing no ortho substituents (2).

EXAMPLE 13 To demonstrate the usefulness of the compounds as antioxidants for gasoline, a sample of catalytically cracked gasoline was used in the ASTM-D-SZS oxidation induction period test. A concentration of 40 mg. of antioxidant per liter of gasoline was used.

Compound: Minutes to failure (1) Blank 141 (2) Bis- 3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide 315 EXAMPLE 14 The use of these compounds in petroleum oils is demonstrated by the ASTM-D-943 oxidation test for turbine oils. The concentration of antioxidant was 0.1%.

Compound: Hours to failure (1) Blank 200 (2) Bis-(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide 800 7 EXAMPLE 15 Concen- Viscosity Stabilizer tration, Increase,

Percent Percent 1- 1 :1 mixture of phenyl-alpha-naphthyl- 2 89 amine and -ethyl-l0,10-diphenylphenazasiline. 2 Bis-(3-rnethy1-4-hydroxy-fi-t-butyl- 2 benzyl) sulfide. 3 Bis-(3-methyl-4-hydroxy-fi-t-butyl- 1 42 benzyl) sulfoxide.

No'lEL-In Example 12. antioxidant A is "Naugawhite" a registered trademark of the United States Rubber Company, bis-(2-l1ydroxy-3 nonyl-fi-methyl phenyl) methane.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A composition consisting essentially of about 0.01 to 5 parts by weight of an antioxidant selected from the group consisting of bis-(3,S-dihydrocarbyl-4-hydroxybenzyl) sulfoxides as represented by the structural formula:

wherein R and R are selected from the group consisting of alkyl, cycloalkyl and aralkyl radicals containing less than 13 carbon atoms, in admixture with parts by weight of organic material normally subject to oxidative deterioration.

2. A composition as in claim 1, wherein the anti oxidant is bis-(3,5-di-t-butyl-4-hydroxybenzyl) sulfoxide.

3. A composition as in claim 1, wherein the antioxidant is bis-(3-methyl-4-hydroxy-S-t-butylbenzyl) sulfoxide.

References Cited UNITED STATES PATENTS 11/1949 Mikeska et al 260-609 3/1961 Long et al 260609 LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, Examiner.

J. E. MOERMOND, M. WEINBLATF,

Assistant Examiners. 

1. A COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 0.01 TO 5 PARTS BY WEIGHT OF AN ANTIOXIDANT SELECTED FROM THE GROUP CONSISTING OF BIX-(3,5-DIHYDROCARBYL-4-HYDROXYBENZYL) SULFOXIDES AS REPRESENTED BY THE STRUCTURAL FORMULA: 